US4792625A - Process for the reduction of organic compounds using alkali formate salts - Google Patents

Process for the reduction of organic compounds using alkali formate salts Download PDF

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Publication number
US4792625A
US4792625A US07/071,643 US7164387A US4792625A US 4792625 A US4792625 A US 4792625A US 7164387 A US7164387 A US 7164387A US 4792625 A US4792625 A US 4792625A
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process according
water
formate
reaction
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Harold Wiener
Shmuel Vandel
Yoel Sasson
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Yissum Research Development Co of Hebrew University of Jerusalem
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Yissum Research Development Co of Hebrew University of Jerusalem
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Assigned to YISSUM RESEARCH DEVELOPMENT COMPANY OF THE HEBREW UNIVERSITY OF JERUSALEM, 46 JABOTINSKY STREET, JERUSALEM, ISRAEL, A ISRAELI CORP. reassignment YISSUM RESEARCH DEVELOPMENT COMPANY OF THE HEBREW UNIVERSITY OF JERUSALEM, 46 JABOTINSKY STREET, JERUSALEM, ISRAEL, A ISRAELI CORP. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: SASSON, YOEL, VANDEL, SHMUEL, WIENER, HAROLD
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
    • C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/18—Carbon
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
    • C07C2523/44—Palladium

Definitions

  • the present invention relates to a process for the reduction of water immisible and sparingly water soluble organic compounds (hereinafter referred to as substantially water insoluble organic compounds).
  • the present invention relates to the reduction of an organic compound containing a reducible group such as a water immiscible or sparingly water soluble aromatic or heteroaromatic compound containing a nitro or azo group, or a water immiscible or sparingly water soluble unsaturated organic compound, comprising contacting said compounds with an aqueous solution of a formic acid salt in the presence of a hydrogenation catalyst and in the substantial absence of a phase transfer catalyst.
  • a reducible group such as a water immiscible or sparingly water soluble aromatic or heteroaromatic compound containing a nitro or azo group, or a water immiscible or sparingly water soluble unsaturated organic compound
  • the process of the present invention is preferably based on the use of alkali formate salts and hydrogenation agents in a transfer hydrogenation reaction, by the action of a supported Group VIII metal or catalyst.
  • This three-phase system consists of an aqueous formate salt solution, an organic, substantially water-immiscible, solution containing the substrate whichis to be reduced and a third solid phase of a Group VIII metal supported catalyst, without the need of using a solvent, high temperatures or a phase transfer catalyst.
  • Catalytic hydrogenation using molecular hydrogen is a well-known field as described, e.g. by Rylander, P. N. "Organic Syntheses with Noble Metal Catalysts", Academic Press: London, 1973, pp. 1-74 and Freifelder, M. "Catalytic Hydrogenation in Organic Synthesis", J. Wiley & Sons, USA, 1978.
  • the use, however, of hydrogen gas suffers from several disadvantages. These include high diffusibility, flammability and explosivity of hydrogen gas, necessitating special equipment in order to avoid fire and explosion hazards. In addition, due to its very low density the transportation of hydrogen gas is carried out in high pressure cylinders and costs are often prohibitive.
  • British Pat. No. 1458633 also discloses a process for dehalogenating water-immiscible aromatic compounds by contacting the said compound with an aqueous solution of a formic acid salt in the presence of a hydrogenation catalyst and a surface active agent or a phase transfer catalyst.
  • German Pat. No. 2536914 discloses a process in which water soluble organic compounds such as nitrosulfonic or carboxylic acid salts are reduced by formate salts in the absence of a surface active agent or a phase transfer catalyst which are unnecessary when only one phase is present. From the above mentioned British patents one can learn that heretofore it was believed and taught that the use of a phase transfer catalyst is essential for reducing water insoluble compounds where two phases are present in contradistinction to said Germany patent from which one would understand that only with water soluble compounds is the use of a phase transfer catalyst not required.
  • nitroaromatic and unsaturated water insoluble compounds can be successfully converted to their respective hydrogenated products by contacting an aqueous solution of a formic acid salt with an organic solution of the substrate in the presence of a hydrogenation catalyst, preferably a supported Group VIII metal catalyst on any inactive support, without the use of any phase transfer catalyst or surface active agent.
  • a hydrogenation catalyst preferably a supported Group VIII metal catalyst on any inactive support
  • This reaction is performed at mild conditions of temperature and pressure and by using the stoichiometric equivalent amount of formate salt without the need of excess of the hydrogenation agent as shown in Reactions 1a and 1b.
  • the process of the invention can be used for all types of reductions which are normally carried out with hydrogen gas and a catalyst.
  • carbon-carbon, carbon-nitrogen and carbon-oxygen multiple bonds may be reduced.
  • This process is, however, especially useful for the reduction of water immiscible or sparingly water soluble nitro or azo aromatic and heteroaromatic ring compounds containing a nitro or azo group and for organic compounds containing unsaturated carbon-carbon bonds.
  • the rings may also contain other substituent groups, for example alkyl, phenyl, phenylalkyl, hydrogen, alkoxy, phenoxy, amino, alkylamino, phenylamino, acylamino, hydroxyalkyl, aminoalkyl, haloalkyl, formyl, a carboxylic ester, cyano, alkyl and arylsulphone among others.
  • substituent groups for example alkyl, phenyl, phenylalkyl, hydrogen, alkoxy, phenoxy, amino, alkylamino, phenylamino, acylamino, hydroxyalkyl, aminoalkyl, haloalkyl, formyl, a carboxylic ester, cyano, alkyl and arylsulphone among others.
  • the pH of the reduction medium may be adjusted as desired in order to achieve pH higher than 7. The preferably pH range is about 7 and about 9.
  • the hydrogen catalyst which can be used are preferably those based on Group VIII metals, but the best results are obtained with palladium on carbon.
  • the reaction is carried out conveniently at temperatures up to 200° C. Operating at atmospheric pressure, temperatures of 60°-130° C. are effective, but the temperatures range 70°-120° C. is preferred.
  • the process could be carried out in organic solvents that are water-insoluble such as toluene, benzene, xylene etc., however, the use of alcohols such as ethanol, propanol, isopropanol or butanol is preferred.
  • reaction may be carried out in the presence of an inert gas such as nitrogen.
  • an inert gas such as nitrogen.
  • This invention also provides a hydrogenation process and is especially useful for users far away from hydrogen sources that must store and transport hydrogen gas in pressurized cylinders.
  • the formic acid salt is preferably an alkali metal salt, but ammonium or trialkyl ammonium formate may also be used. It has also been found that adjusting the amounts of water present can be used to enhance the obtaining of high conversion and rates.
  • the process is preferrably carried out wherein the water to formate molar ratio is about 0.5:1 to about 5:1 and especially preferred is a water to formate molar ratio of about 1:1 to about 3:1.
  • the molar water to formate ratio can be optimized for the hydrogenation process and if the appropriate ratio is used the reduction process is performed at low temperatures at atmospheric pressures and in the absence of any surface active agent and/or phase transfer catalyst. As seen in Table 1 the optimal water to formate ratio on a molar basis is about 2.7.
  • reactions may be performed in different water to formate ratios, but higher temperatures and/or longer times are required to reach complete conversion when low formate concentrations are used.
  • British Pat. No. 1457608 uses in the examples therein water to formate ratios of about 5.5-11.5.
  • sodium formate as hydrogen donor.
  • Potassium formate has shown higher activity in comparison to sodium formate regarding both rates and final conversion as can be seen from Table 2.
  • the bicarbonate resulting from the reaction may be recycled by means of formic acid to the formate salt avoiding the use of new formate salt in each new batch process reaction (Reaction 3).
  • the resulting bicarbonate is partially transformed to carbonate (Reaction 4) depending on the temperatures applied in the process, but it also could be recycled as stated before by means of formic acid (Reaction 5).
  • the formate salt may be produced by any of the processes known in the art (Reaction 6-8) or by hydrogenation of bicarbonate as disclosed in Israel Specification 75580 (Reaction 9).
  • reaction 1 can be recycled after reaction to formate by the addition of formic acid (reaction 3-5).
  • formic acid can be added to the basic solution of bicarbonate/carbonate/formate while the reaction is proceeding, thus always maintaining a definite amount of bicarbonate/carbonate in solution.
  • the reaction may proceed with a fixed amount of formate/bicarbonate/carbonate and adding formic acid dropwise allows for the in situ generation of formate by reaction with carbonate and/or bicarbonate. It is preferred in this process to always maintain an excess amount of bicarbonate in order to maintain a basic pH.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US07/071,643 1986-07-31 1987-07-09 Process for the reduction of organic compounds using alkali formate salts Expired - Fee Related US4792625A (en)

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IL79573A IL79573A0 (enrdf_load_stackoverflow) 1986-07-31 1986-07-31
IL79573 1986-07-31

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4910343A (en) * 1988-09-20 1990-03-20 W. R. Grace & Co.-Conn. Nitroamines
US5336808A (en) * 1990-12-10 1994-08-09 Occidental Chemical Corporation Process for the preparation of 3,5-diaminobenzotrifluoride
WO1995021143A3 (en) * 1994-02-04 1995-11-02 Charles J Rogers Methods for the synthesis of chemical compounds
JP3110775B2 (ja) 1991-02-06 2000-11-20 広栄化学工業株式会社 アミノアントラキノン類の製造方法
WO2002020442A1 (de) * 2000-09-06 2002-03-14 Merck Patent Gmbh Verfahren zur hydrierung von c-c-doppelbindungen
US20220111357A1 (en) * 2019-02-08 2022-04-14 Evonik Operations Gmbh Reduction of organic compounds

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1457608A (en) * 1974-09-17 1976-12-08 Ici Ltd Reduction process
GB1458633A (en) * 1974-09-17 1976-12-15 Ici Ltd Process for dehalogenating aromatic compounds

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1457608A (en) * 1974-09-17 1976-12-08 Ici Ltd Reduction process
GB1458633A (en) * 1974-09-17 1976-12-15 Ici Ltd Process for dehalogenating aromatic compounds

Non-Patent Citations (9)

* Cited by examiner, † Cited by third party
Title
Chemical Abstract 101:6560h (1984). *
Chemical Abstract 77:74590d (1972). *
Chemical Abstract 87:22732p (1976). *
Chemical Abstract 87:5533g (1977). *
Chemical Abstract 96:122308j (1981). *
Chemical Abstract 98:125331p (1982). *
Chemical Abstract 98:16244s (1982). *
Entwistle et al, J.C.S. Parkin I, pp. 443 444 (1977). *
Entwistle et al, J.C.S. Parkin I, pp. 443-444 (1977).

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4910343A (en) * 1988-09-20 1990-03-20 W. R. Grace & Co.-Conn. Nitroamines
US5336808A (en) * 1990-12-10 1994-08-09 Occidental Chemical Corporation Process for the preparation of 3,5-diaminobenzotrifluoride
JP3110775B2 (ja) 1991-02-06 2000-11-20 広栄化学工業株式会社 アミノアントラキノン類の製造方法
WO1995021143A3 (en) * 1994-02-04 1995-11-02 Charles J Rogers Methods for the synthesis of chemical compounds
WO2002020442A1 (de) * 2000-09-06 2002-03-14 Merck Patent Gmbh Verfahren zur hydrierung von c-c-doppelbindungen
US20040030150A1 (en) * 2000-09-06 2004-02-12 Stefan Lehmann Method for hydrogenating c-c double bonds
US7094905B2 (en) 2000-09-06 2006-08-22 Merck Patent Gmbh Process for the hydrogenation of C—C double bonds
US20220111357A1 (en) * 2019-02-08 2022-04-14 Evonik Operations Gmbh Reduction of organic compounds

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IL79573A0 (enrdf_load_stackoverflow) 1986-10-31

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